Reducing sugar product and method of making same



'Patented Dec. 15. 1942 Search Room REDUCING SUGAR PRODUCT AND METHOD OFMAKING SAME "ba'vid P. Langlois, Decatur, 111., asslgnor to A. E; StaleyManufacturing Company, Decatur, 111.. a. corporation of Delaware NoDravving. Application May 21.1940,

, Serial No. 337,487

Claims. I

The presentinventlon relatesto the production of an ediblesugarhiassecuite of the-reducing type and hasparticular reference ta-conversion otstarch into. a solid massecuite productvincor porating,conversion by-products, .the productbr, I p fi en e; h r e bx; ch the,product lsiormed involving a dual typeofconversion bywhicn-the'production of unpleasant massecuite by-productsisavoided.

A principal object of the invention is the production-without yield-lossand, by a dual type 01 te co rsion-oi. -a .-mn. e u1te which sets, upas, cco id ys le .8 of a ep able taste which doesncl.

An. addition, obiect. of. the; invent ng is: se m t ergch m beeum Mommascid conve ,2 Produc r m-M t ew! is str sejdjenum ents demo New "en..:mhi9m t oom amn..- opeseqm t e s i-e or h s-m c. ed nlelw eifltvfivs ehem hetthere-isproduced a-mother 1 1mm,;-

dextrcseequivhl t e elw ori betvieenmindism this mother liquonthenbeing-concentrated;

crystallized initss'ientirety; toformjaa solid rnass'ecuitewhich-flncorporates all or the non-1 crystalline by-productsot; theconversion -oper-- ation.

sun another obiectlisto produce a-novel type v;

01' starch conversion, massecuiteofacceptable' taste and having.crystallization characteristics which 'malre the product particularly;desirable for many uses withoutthe usual centriiiiz'lnsbh erationsemployedheretofore in theiproductiofiof ediblesugar. i

These and other objects will be observed upon a considerationof-thefollowing description dt'a preferredembodin'ient oi the invention.-

= Various types or starch convrsion products have been known heretofore.on s: the niost commonly: used oonversion fvpifqducts known" as "'onrctrodrs' g ucos "Which*b0n-'-' sists of an acigbconverted syrup ofintermediate dextrose equ ii'relen'lz' content, the Oi crystallizing"and of relatively, inild sweetness. When corn starch is used to produce. the glucose the product often is referred to as "corn syrupunmixed. Nonnally, the dextrose equivalent content of glucose isof theorder of 40 to per cent, although both lower and higher "purity" glucosehave been used to some extent. If the acid conversion step is carried tosuch an extent that the dextrose equivalent content is oi the e lle iish .-e re ew -h sol dify so. thetthe us e c mpi'tefl emcther liquo Mqmcmin st m zhe sila-t r-pmd t l nmhermpe s e,,v m LA welt-em are:zzsisze; snanu qste 1.93s, sp eitezien mappmaa. th re ismwfl q lemn tzm'c e Yeme .w biectinmnnsecld rconve an attractive taste .and requires .nopurging on centrifuging itifltd'or edible purposesn r d c ehe-newmas'secuite, astarchsuspension is subjected to acid hydrolysis:inthe mannermistomaxilyemployedin the manufacture of confectioners'giucose; $1116: acid hydrolysis is carried out to produce aJJlqubrhaving adex trose equivalent content-oi morethan 40 per cent andpreferably between Lani-60. w]? cent. The hydrolysisis stopped beforeundue quantities of undesirableztaste 'andcolor-forming constituents areproduced. A starch suspens'ionof a density corresponding to-about10to20'lBaum F.)

may be employed in the conversion by acid. Where the acid conversion iscarried to a relatively high extent, it is preferred to use a relativelylight starch suspension-since under such conditions there is lesstendency for the development of a. hydrol taste than where a moreconcentrated starch suspension is utilized.

The starch suspension is mixed with aqueous hydrochloric acid containingabout 6.2 pounds of HCl per 1,000 gallons of the suspension, the mixturebeing boiled at atmospheric pressure until thoroughly pasted. In thepasting step the mixture may have a pH of about 1.6 to 1.8.

The pasting operation is followed by subjecting the starch to a pressureconditioning and conversion step to the extent necessary to produce aliquor having a dextrose equivalent content of more than about 40 percent. This operation involves the use of a pressure converter having asteam injector by which the temperature of the mixture is brought to apoint corresponding to about 35 pounds gauge pressure. Preferably, theacid conversion step is controlled to produce a liquor having a dextroseequivalent content of between 45 and 55 per cent.

After the completion of the acid conversion the resulting liquor istreated with a sufficient quantity of sodium carbonate to provide a pHof about 4.6 to 5.0. The neutralized liquor is filtered and decolorizedby treatment with bone char or activated carbon. After the carbontreatment the liquor is concentrated in a vacuum evaporator to betweenand 35 Baum. Preferably, this concentration is to between and Baum.

Following the acid conversion and clarification as described, thesubsequently concentrated liquor then is subjected to treatment withasa'cchaiifying enzyme of the fungus type having maltose and diastaticactivity. The enzymatic treatment is carried out at'a temperaturefavorable to the action of the selected enzyme. Fungusenzymes generallyhave an optimum operating temperature of between 110 and 160 R, thistemperature usually being controlled to between'125" F. and 145 F. 3 l

For secondary conversion with the fungus enzyme, the pH of thellquorisbrought to about 5.5, and a fungus enzyme containing both diastase andmaltase isadded in such amount that the dextrose equivalent content ofthe liquor' is raised t between 80 and 90 cf centfthetihie 0 p mix tiixothe' yield obtained from the conversion of the treatment necessary toproduoe' h dexifros'e equivalent content of this order usii'allybeingbetween 48 and 96 hours where oer-ti) 0.8per' cent, of the enzymepreparation ifu'tilizd. -It will be understood that it is a purifiedenzyme so that very little foreign matter is added to the resultingsugar product. The time and quantity of enzyme'employed in the processnaturally will dependto some extent upon the extent of the acidconversion, the nature of the particular enzyme employed and theextentto which the secondary conversion is carried, and

the other factors involved arecontrolled so as to provide for thesecondaryconversion within less than 100 hours. i

There are a number of enzyme preparations available commercially inpurified form which will provide the desired maltase and diastaseactivity. The production of fungus enzymes usually is effected byinoculating wet sterilized bran with spores of the desired fungus anddrying the bran at a mild temperature after four or five days growth ofthe culture. The resulting enzyme may be purified by extraction from thebran with water and precipitates from the water with alcohol. have beenemployed in the operation of the process are Aspergillus oryzce,Aspergillus flames. Asperg'illns nicer, Aspergillus wentii, Moniliasitophila, Rhizopus nigricans, and Rhizopu tritz'ci.

After completion of the enzymatic conversion preferred to employ Amongthe fungi enzymes which Lib the liquor is again decolorized by the useof bone char or activated carbon and the pH of the liquor preferably isadjusted to 4.8 to 5.0. Thereafter the liquor is concentrated toapproximately Baum by vacuum evaporation.

At this concentration and with a dextrose equivalent'content of betweenand per cent the resulting massecuite is seeded with crystallinedextrose hydrate or anhydrous dextrose or both, and stirred untilconsiderable crystallization has occurred. After the partialcrystallization the massecuite next is poured into molds and allowed tocrystallize as a solid mass. The solid massecuite then is ready for useand may be brought into a form more easily handled by chipping orshaving the solid material into portions of small size.

The analytical data given herein in terms of per cent are calculated onthe dry substance of the materials as determined by the methods ofanalysis set forth in the copending application referredto above, nowPatent No. 2,201,609. In that application particular care was taken toprevent the acid and enzyme conversion of the syrup from going to thepoint of crystallizing. Crystallization was considered a detriment andwas'avoided by stopping the enzyme and acid conversions short of thepoint at which crystalline materials tend to separate out of the syrup.In accordance with thepresent process the acid conversion is stoppedbe'f'or'e the point is reached at which crystallization occurs, but theenzyme conversion definitely is carried past the critical point at whichthe massecuite' becomes crystallizable into a solid mass incorporatingcertain b-y-productsof the acid and enzyme conversions.

Apparently, these by-products areof diflerent chemical nature than theby-products obtained heretofore-fin the production of crystallizablemasses. Evidence of this difference is to be had inthe fact that inaccordance with the present process these by-products are notbitter'tasting and-do not have the tasteor color characteristicsof-a-hydrol. By solidifying. the entire reaction is L00 per cent and atthe "same time theproduct is'quiteediblen Imprevious dextrose sugarproducing processes there has been a. definite loss due to the necessityof purging the masseculte to produce an edible product. The liquidpurged from crystalline masses of dextrose hydrate or anhydrousdextroseas produced heretofore was dark. colored and of extremely bitter taste.

The particular nature of the by-products in thamassecuite other thandextrose lend to the product certain advantages from the standpoints ofcrystallization characteristics, stability, texture,- taste; rate'ofsolubility, blending characteristics and".otherw-ise, which make theproduct superior. to previously known materials for various uses. Forinstance, the novel massecuite is usable in, larger quantities in jamsand jellies than arerefinecl dextrose hydrates or anhydrous dextrose.

Asa example of the operation of the process a starch suspension wassubjected to acid hydrolysis in the usual manner to produce a syruphaving a dextrose equivalent content of 48.4. Three liters of this syrupconcentrated to 525 Brix and containing 1900 grams of dry substance wastreated with 3.8 grams of fungus enzyme at F. The dextrose equivalentcontent of the syrup increased rapidly at first and more slowly towardthe end of the process until at 118 hours the dextrose equivalentcontent of the syrup had reached 87.8 per cent. The dextrose content ofthis material was 81.0. The conversion liquor then was treated with 1.5per cent of activated carbon at 150 F. for minutes. After filtration thesyrup was concentrated to approximately 45 Baurn (85 per cent drysubstance). The concentrated massecuite was seeded at 130 F. with 1 percent by weight of dextrose hydrate and the seeded massecuite was stirredand cooled to room temperature. the massecuite had crystallized to aconsiderable extent but still could be poured. It was poured into moldsand allowed to stand over night, during which time the massecuite setinto a solid After about 4 hours stirring l0 extent that there is havinga dextrose equivalent content in excess of 80 to about 95, concentratingthe resulting liquor, and subjecting the concentrated liquor to acrystallization,operation in which the entire mass of material sets intoa solid, white product of edible nature.

2. The process for producing an edible solid massecuite, which comprisessubjecting a starch suspension in water to acid hydrolysis to such anproduced a conversion liquor having a dextrose equivalent content ofmore than 40and less than that at which undesirable taste andcolor-imparting constituents are formed, subjecting the acid conversionliquor to i -S T y zed or solidified massecuite the saccharifying actionof a purified fungus enwas removed from the molds and shaved into finelydivided material.

As another example of the process a starch conversion liquor of 6 .2 percent dextrose equivalent content was produced by acid conversion d of astarch suspension of a dilute nature. This liquor was concentrated toabout52 Brix and subjected to treatment with 0.l percent purified fungusenzyme having maltase and diastase activity at a temperature of 130 thesyrup had a dextrose equivalent content of 77.1 per cent. At 67 hoursthe syrup had a dextrose equivalent content of 80.2 per cent. At 115hours the enzyme conversion was stopped and th syrup had a dextrosecontent of 76.8 per cent. filtered, concentrated and crystallized as dewscribed before to produce a solid, white, sweetq tasting sugar.

One advantage of the improved massecuite over the purified dextroseknown heretofore is its substantially quicker rate .of solubility. In.-the case of dextrose syrups produced by acid hyizyme to produce a finalconversion liquor having a dextrose equivalent content between 80 and 95per cent, concentrating the final conversion liquor to the extentnecessary for crystallization, producing from the resulting concentratedliquor a solid massecuite incorporating the byproducts of the acid andenzyme conversion operations.

3. The process of producing a solid starch con- After 43 hours 5'version reaction mixture of edible nature, which comprises hydrolyzing astarch suspension with acid to. produce a.swcet-tasting liquor having adextrose equivalent content between to around to per cent free from.undue quantities of equivalent 0011mm sounde'sirabla taste andcolor-imparting constit- 86. The converted syrup also had a dextrose,The massecuite was uents, treating the acid-converted liquor with afungus enzyme to the extent necessary to produce a. liquor having adextrose equivalent content of more than 80 to about 95 per cent, and

"35 crystallizing the entire conversion mass to form "a white, ediblesolid.

,4. The process of producing an edible solid starch conversion sugarproduct, which comprises subjecting a starch suspension in waterdrolysis' there is a greater tendency tOWaI'dQT-YS' 40 to acidhydrolysis to the extent necessary to protallization than with a sugarproduct produced as described herein wher the dextrose-contents oi thetwo types of materialsare comparable, :How- 1, ever, the massecuite ofthe l'present invention' does readily set up no purification. While thedextrosereqiuyalent' content of the improved product vary between 80 and92 per cent, thedextrose content will be foundto be between and 90;Below a dextrose equivalent content of "about per: cent a massecuitewill not set up into a permanent,'f dry, crystalline mass, even thoughconcentrated to around per cent solids.

It will be seen that th process and product may be varied considerablywithout departing from the scope of the invention as defined in theappended claims.

I claim: 7

1. The process of producing sugar products, which comprises subjecting astarch suspension in water to acid hydrolysis to produce an edible.non-crystallizable liquor having a dextrose equivalent content in excessof 40 up to 55 to 60 per cent, subjecting the resulting liquor to thesaccharifying effect of a fungus enzyme having maltase and diastaticactivity to produce a liquor duce a non-crystallizing sweet-tastingcolorless liquor having a dextrose equivalent content in excess of 40per cent, subjecting the resulting liquor to the action of a fungusenzyme having into a Solid mass s 'i '4 maltaseand diastjanc activity toproduce a liqnor of a dextrose equivalent content of at least 80 toabout per cent which will crystallize into a solid mass whenconcentrated, said liquor being free from undue quantities ofundesirable taste-imparting constituents, and crystallizing saidliquorinto a solid mass incorporating the by-products of the acid andenzyme conversions.

5. An edible starch conversion product, comprising a solid mass composedof crystallized 55 reducing sugarshaving incorporated therein byproductsof acid and enzyme conversions, said product resulting from anintermediate conversion of a starch suspension with an acid having adextroseeq'uivalent content of between 40 to on about 55 to 60 per centand a final conversion of the resulting liquor with a fungus enzymehaving a dextrose equivalent content of between 80 and 95, being quicklysoluble in water, and being substantially free of undesirable taste andcolorcfi imparting constituents.

DAVID P. LANGLOIS.

